Science of the Total Environment 876 (2023) 162840

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Science of the Total Environment

journal homepage: www.elsevier.com/locate/scitotenv

Application of novel polypyrrole/melamine foam auxiliary electrode in

promoting electrokinetic remediation of Cr(VI)-contaminated soil
⁎
Zhengjun Qu a, Lihui Huang a, , Mengmeng Guo b, Ting Sun a, Xiaoshen Xu a, Zhenhui Gao c
a
Shandong Key Laboratory of Water Pollution Control and Resource Reuse, School of Environmental Science and Engineering, Shandong University, Qingdao 266237, China
b
Jinan Ecological and Environmental Monitoring Center, Jinan 250000, China
c
Institute of Eco-Environmental Forensics of Shandong University, Qingdao 266237, China

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• PPy-MF had a positive effect on both the

current intensity and electric field distri-
bution of EKR.
• PPy-MF could prevent the development of
an alkali front in EKR.
• The use of PPy-MF improved the removal
rate of total chromium and Cr(VI).
• The combination of PPy-MF enhanced
electromigration and its adsorption reduc-
tion of Cr(VI) is the key mechanism.

A R T I C L E I N F O A B S T R A C T

Editor: Baoliang Chen There is an urgent need for an effective remediation method for soil that has been heavily polluted by heavy metals.
The application of polypyrrole/melamine foam (PPy-MF) auxiliary electrode in the traditional electrokinetic remedi-
Keywords: ation (EKR) system greatly increased the removal efficiency of Cr(VI) by enhancing electrical conductivity in soil, cur-
Electrokinetic remediation
rent strength of the system, and optimized the distribution of the electric field. Because of the strong Lewis acid
Auxiliary electrode
property of PPy, it can inhibit the development of an alkali front in the EKR process in addition to buffering the polar-
Polypyrrole
Cr(VI)-contaminated soil
ization of the catholyte's pH. Application of PPy-MF auxiliary electrode increased the removal rates of both total Cr and
Electric field simulation Cr(VI) by 34.5 % and 11.5 %, 26.1 % and 10.1 %, and 25.2 % and 9.9 % at 30 V, 45 V, and 60 V voltage conditions,
respectively, compared with traditional EKR, and improved the overall soil Cr(VI) reduction rate. Additionally, due to
the effective Cr(VI) adsorption reduction of PPy-MF, the total Cr concentration in the anolyte was significantly de-
creased. This study provides a facile and effective way in remediation of Cr(VI)-contaminated soils.

1. Introduction
Human activities in metallurgical industry, textile industry, and elec-
tronic production industry aggravated soil contamination of heavy metal
chromium (Cr), threatening human and environmental health (Li et al.,
2022a; Li et al., 2022c; Liu et al., 2023; Xie et al., 2022; Yang et al., 2022;
⁎ Corresponding author.
E-mail address: huanglihui409@126.com (L. Huang).
Zhao et al., 2023). Cr causes acute neurotoxicity and is highly mutagenic
(Yang et al., 2023). Cr in soil is accumulated by soil organisms, which ad-
versely affects their survival and reproduction. In addition, Cr in soil can ac-
cumulate through the food chain, posing a potential threat to human health
(Santos et al., 2023). Cr(VI) has higher toxicity and mobility than Cr(III) in
soils (Chang et al., 2023; Yang et al., 2022; Zhang et al., 2022b). Cr(III)
readily forms chromite and Cr-containing silicate minerals in the soil,
while Cr(VI) and soil do not interact easily and dissolve mainly in soil
pore water (Ao et al., 2022). Cr(VI) can cross the cell membrane to destroy

http://dx.doi.org/10.1016/j.scitotenv.2023.162840
Received 9 December 2022; Received in revised form 22 February 2023; Accepted 9 March 2023
Available online 15 March 2023
0048-9697/© 2023 Elsevier B.V. All rights reserved.
Z. Qu et al.
protein structure and genetic information leading to cell inactivation, while
Cr(III) cannot penetrate the cell membrane (Narayani and Shetty, 2013;
Zhang et al., 2021). As a result, the majority of research on remediation
techniques concentrates on converting Cr(VI) to Cr(III) and limiting its mo-
bility, but Cr(III) is still an ecological risk in complex soil environments (Liu
et al., 2020; Xie et al., 2022; Zhao et al., 2023). Effective separation and ex-
traction of heavy metals from soil and subsequent resource usage may be
more promising options, such as electrokinetic remediation (EKR) (Yan
et al., 2023; Zhao et al., 2023; Zheng et al., 2022), chemical leaching
(Park et al., 2021; Xie et al., 2022; Zhang et al., 2022c), phytoremediation
(Li et al., 2023; Liu et al., 2022; Shi et al., 2023), and thermal desorption
(Yue et al., 2022).
Chemical leaching is remarkably effective in treating heavily contami-
nated soils, but the use of excessive amounts of chemicals leads to irrepara-
ble harm to the physicochemical characteristics and ecological functions of
the soil, including the loss of significant amounts of nutrients that are nec-
essary for agricultural production (Yue et al., 2022), the risk of secondary
contamination from chemical residues (Zhao et al., 2021), and the high
cost of disposing of waste liquids from drenching (Xie et al., 2022; Zhang
et al., 2022c). Phytoremediation skillfully takes use of the physiological
characteristics of plants, especially hyperaccumulators that not only can
hyperaccumulate heavy metals but also keep them at high concentration
levels (Jin et al., 2021; Shi et al., 2023). Phytoremediation is without a
doubt the most natural remediation technique, but due to the expense of
lengthy remediation time and the impact of numerous unstable factors on
the results, it has faced some difficulties in becoming a successful technique
for remediating heavy metal-contaminated soil (Song et al., 2022; Wang
et al., 2021b). Thermal desorption, which is commonly used to remove vol-
atile organic compounds (VOCs) from, is mostly employed for heavy metals
with low boiling points (such as mercury) in the realm of soil heavy metal
remediation (Cho et al., 2021; Park et al., 2015; Zhao et al., 2019). The
thermal desorption method decreases the possibility of secondary contam-
ination. However, due to the stringent specifications for the treatment
equipment and the restrictions of the suitable operating circumstances,
this approach still has some potential for improvement in the area of soil
heavy metal remediation. EKR is unquestionably the best technology for
remediating heavy metal-contaminated soil among these existed technolo-
gies due to the higher removal efficiency and broad applicability. However,
the side effects (thermal effect, Crystallization effect, electrode corrosion,
and focusing effect) of the traditional EKR process severely hampered the
efficiency of EKR (Wen et al., 2021). To improve EKR, some studies have fo-
cused on combined primary and auxiliary electrode systems (including the
third electrode enhanced EKR), which enhance EKR efficiency by utilizing
the excellent electrochemical properties and the redox ability of the
auxiliary electrode (Wang et al., 2019a; Wang et al., 2019b; Yan and
Kirkelund, 2022; Zhao et al., 2021; Zhao et al., 2023). Using tungsten disul-
fide loaded with iron oxychloride as an auxiliary electrode, Zhao et al.
(2021) and Zhao et al. (2023) demonstrated analytically that S doping en-
hances the electrochemical performance of the auxiliary electrode more
than W doping in terms of chlorine vacancies and confirmed that the
main causes of the reduction of Cr(VI) are Fe2+ and S2−, whereas the
reduction of Fe3+ to Fe2+ is attributed to the reduction of W4+ and the
loss of Cl. Our previous studies found that auxiliary electrodes made of
polyaniline/nonwoven fabric and polypyrrole/linen fabric could opti-
mize the distribution of the electric field with an increase in the migra-
tion and enrichment of Cr(VI) ions and provide plenty of active sites for
the adsorption and reduction of Cr(VI) (Wang et al., 2019a; Wang et al.,
2019b). There is no doubt that auxiliary electrodes play an important
role in improving the efficiency of EKR. However, the mechanisms of
auxiliary electrodes in affecting distributions of the electric field,
changes in the electric current, and the precise process of EKR perfor-
mance in complex soil environments remain largely unknown. Particularly,
conductive polymer-based auxiliary electrodes have been less studied, and
the effects and processes in real soil settings are not yet known, so it is
necessary to deploy them to real polluted soils to analyze how they
enhance EKR.
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Science of the Total Environment 876 (2023) 162840
As a pseudocapacitive material commonly employed in supercapacitors,
PPy is widely utilized in wearable electronic devices, electrochemical en-
ergy storage devices, and biomaterials (Lima et al., 2018; Mu et al., 2023;
Wu et al., 2022). Moreover, it has attracted widespread attention in the
field of catalysts, adsorbents, and reducing agents (Abdi et al., 2017;
Chen et al., 2019; Li et al., 2022b). Depending on the PPy functional groups'
abundance, environmental stability, and ease of availability, adsorbents
made of PPy have been extensively studied. The majority of research has
demonstrated that PPy-based adsorbents have conspicuous adsorption
properties for chromate in solution, and they can convert Cr(VI) to Cr(III)
(Li et al., 2022b; Xu et al., 2019). Based on the outstanding electrochemical
and physicochemical qualities of PPy, it is a viable option to utilize it for the
fabrication of auxiliary electrodes for EKR. By π-π stacking, PPy particles
will clump together and the specific surface area will be decreased. In this
work, chemically stable, high-porosity melamine foam (MF) was used as
the support skeleton to prevent unequal distribution of PPy (Sun et al.,
2019; Xu et al., 2019).
Polypyrrole/melamine foam (PPy-MF) auxiliary electrode was synthe-
sized by in situ polymerization on MF for the construction of a novel EKR
system with primary and auxiliary electrode configurations, aiming to in-
vestigate the operational mechanism of PPy-MF-assisted EKR. Herein,
PPy-MF was not only acted as an adsorbent for the adsorption of Cr(VI)
but also an auxiliary electrode for EKR systems. Specifically, we aim to
(i) study the effects of various preparation circumstances (surfactant ratio,
pyrrole monomer dosage) on the adsorption performance, and explain the
adsorption behavior according to the adsorption performance, (ii) investi-
gate the impact of the electrochemical performance and adsorption perfor-
mance of the PPy-MF auxiliary electrode on EKR, (iii) determine the
mechanisms of PPy-MF in promoting Cr(VI) migration and enrichment,
(iv) elucidate the role for the enhancement of Cr(VI) reduction by EKR by
PPy-MF.
2. Materials and methods
2.1. Materials and reagents
Melamine foam (MF) was provided by Chengdu Minnemin New Mate-
rial Technology Co., Ltd. (Chengdu, China). Pyrrole (Py) monomer, sodium
dodecyl benzene sulfonate (SDBS), and hexadecyl trimethyl ammonium
bromide (CTAB) were purchased from Shanghai Macklin Biochemical
Co., Ltd. (Shanghai, China). Potassium dichromate (K2Cr2O7), ferric chlo-
ride hexahydrate (FeCl3·6H2O), acetone (CH3COCH3), diphenylcarbazide
(C13H14N4O) obtained from Sinopharm Chemical Reagent Co., Ltd.
(Shanghai, China).
In the Supplementary Material, the collection and pretreatment of the
experimental soil can be found in Text S1. The physicochemical properties
of the soils are listed in Table S1, and the oxide and monomer contents of
the spiked soil were measured by X-ray fluorescence spectrometry (XRF,
Panalytical Axios, Netherlands) as shown in Table S2. After a period of
soil stabilization, the total Cr and Cr(VI) concentrations were
596.45 mg/kg and 384.06 mg/kg, respectively, indicating the existence
of certain chemical reduction processes during soil stabilization.
2.2. Preparation and characterization of PPy-MF
The method for the preparation of polypyrrole-melamine foam (PPy-
MF) is referred to the preparation method of our research group PPy
(Text S2 of Supplementary Material) (Wang et al., 2019b). The characteri-
zation method of PPy-MF can be found in the Text S3 of the Supplementary
Material.
2.3. Batch adsorption
The molar ratio of FeCl3 and pyrrole was about 2.6, the concentration of
FeCl3 was maintained at 0.5 M, and the dosage of pyrrole was set to 1, 1.5,
2, and 2.5 mL to investigate the effects of the ratio of CTAB and SDBS and
Z. Qu et al.
the dosage of pyrrole monomer on the adsorption capacity. By the instruc-
tions in Section 2.2, PPy-MF was prepared, and tests to remove Cr(VI) via
adsorption were conducted. The adsorption equilibrium was achieved by
oscillating the PPy-MF at 200 rpm for 24 h with a horizontal oscillator in
a conical flask holding 200 mL of Cr(VI) ion at a concentration of
500 mg/L, respectively. After the adsorption, the adsorption capacity of
each PPy-MF was calculated by Eq. (1):
q ¼ ðC 0  C t Þ  V=m (1)
where C0 and Ct are the initial concentration and time concentration (in
mg/L) of Cr(VI), respectively; q (mg/g), m (g), and V (L) denote the quan-
tity of metal ions adsorbed per unit mass of adsorbent, the mass of adsor-
bent, and the volume of sample, respectively.
The adsorbent was placed in a conical flask with a specific concentra-
tion of Cr(VI), and the Cr(VI) concentration was measured by sampling at
a specific time interval. The adsorption curve was then made, and a kinetic
analysis was carried out, to further assess the adsorption performance of the
adsorbent with the maximum adsorption capacity.
2.4. Electrokinetic remediation setup
The EKR device is 35 cm × 10 cm × 10 cm in size, and it is made en-
tirely of plexiglass, as is the perforated partition. In the middle is the soil
chamber, and on both sides of the soil chamber are the anode and cathode
chambers, respectively (Fig. S1). The soil chamber includes five equal sec-
tions, which are marked as S1, S2, S3, S4, and S5 from the anode to the
cathode, respectively. In each section, a graphite rod (D = 5 mm, L =
12 cm) is set up to measure the potential difference between the anode
and the potential electrode, and the electrode liquid (A, C) is taken from
the groove of PPy. The inert electrode graphite rods (D = 1 cm, L =
13 cm) are fixed in the groove of the PPy-MF auxiliary electrodes and
connected to the regulated DC power supply through the wire. The elec-
trode chambers are filled with PPy-MF auxiliary electrodes that can be
inserted into the graphite electrode rod (GR). Two porous Plexiglas
plates with filter paper are used as separation partitions to divide the soil
chamber from the electrode chamber and keep soil particles out of the elec-
trode chamber. The partitions are installed by sliding slots to enhance their
stability.
2.5. Electrokinetic remediation experimental conditions
A stable DC voltage was supplied to the EKR setup using a regulated DC
power supply. The operating parameters for the EKR experiments, which
were carried out over the course of four days under various operating con-
ditions with various electrode combination configurations and voltage gra-
dients, are displayed in Table S3. Voltage gradients of 1, 1.5, and 2 V/cm
were set, and the EKR experiments were labeled as EK1, EK2, EK3, EK4,
EK5, and EK6, while a control group without electricity was set and
designated as NEK. This investigation was done to determine the impact
of PPy-MF on the effect of EKR under different voltage gradients. The sup-
plementary material's Text S4 and Text S5 include details about the precise
operations carried out and the pertinent analytical techniques during the
EKR experiments.
2.6. Sequential extraction of Cr
The experimental soil samples were extracted using the modified BCR
sequential extraction technique (Song et al., 2023). Each soil sample can
be divided into four fractions: exchangeable fraction (F1, weak binding
ability to soil, strong migration and transformation ability, and the greatest
environmental hazard), reducible fraction (F2, easy to release under reduc-
ing conditions), oxidizable fraction (F3, easy to decompose and release in
oxidizing environment), and residual fraction (F4, the most stable in soil en-
vironment, the least environmental hazard).
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Science of the Total Environment 876 (2023) 162840
3. Results and discussion
3.1. Characterization of PPy-MF
The PPy-MF preparation procedure, scanning electron microscopy
(SEM), and transmission electron microscopy (TEM) images are displayed
in Fig. 1. PPy-MF was prepared by the polymerization of Fe3+ oxidized pyr-
role monomer on MF (Fig. 1a). The color of MF changed from white to
black. The pore size of MF was between 100 and 200 μm. MF had a uniform
pore distribution and a rich three-dimensional mesh structure. The longitu-
dinal, smooth, and without attached impurities surface of the MF skeleton
provides plenty of sites for the deposition of polypyrrole (Fig. 1b-d). The in-
clusion of PPy particles reduced the MF's pore size at a certain degree but
not changed the overall skeleton structure, which had little impact on the
contact reaction between the internal PPy and solution. The PPy particles
of different sizes were connected by π-π forces forming a randomly distrib-
uted PPy attachment layer on the surface of the MF skeleton. The deposi-
tion of PPy particles increased the surface roughness of MF without
significant agglomeration, which was beneficial to the adsorption of
heavy metal ions. The PPy particles on the PPy-MF samples were spherical,
firmly packed, and evenly dispersed (Fig. 1e-g). Compared with MF, PPy-
MF not only has a clearly visible porous structure but also has a dense dis-
tribution of spherical PPy particles exposed on the surface, providing a
good platform for heavy metal ion adsorption. A research using TEM re-
vealed that PPy particles had a propensity to agglomerate, which may
weaken PPy-MFs mechanical strength and negatively impact its
electrochemical performance (Qu et al., 2020). The PPy particles were
comparatively evenly distributed on the MF (Fig. 1h-j). A plausible explana-
tion was that the stabilizing effects of the surfactant SDBS and CTAB soft
templates reduced the tendency of rupture and agglomeration during the
in-situ polymerization of PPy (Sun et al., 2014). Energy dispersive X-ray
(EDX) of PPy-MF showed that elemental Cl was doped into PPy-MF by ox-
idizing pyrrole monomer via FeCl3.6H2O (Fig. S2).
The FTIR analysis of PPy-MF is shown in Fig. S3. The characteristic
peaks in the original MF at 809, 1140, 1340, 1480, and 1550 cm−1
correspond to the triazine ring's bending mode, the stretching vibration of
the C\\O bond, the bending of the C\\H bond, the stretching of the C\\N
bond, and the stretching of the C_N bond, respectively (Pinto et al.,
2018; Stolz et al., 2016; Zuo et al., 2023). For pure PPy, the characteristic
peaks at 1549 and 1461 cm−1 were attributed to the stretching vibration
of the C_C bond and C\\N bond in the pyrrole ring (He et al., 2022).
The characteristic peaks at 1320 and 1050 cm−1 were due to the in-plane
vibration absorption peaks of conjugated C\\N and C\\H bonds,
respectively (Abdi et al., 2017; Ren et al., 2022; Wu et al., 2022). The
characteristic peak at 910 cm−1 reflected the out-of-plane C\\H deforma-
tion vibration in the bipolaron structure (Minisy et al., 2019). The FTIR
spectra of PPy-MF (1546, 1462, 1318, 1048, and 899 cm−1) showed the
characteristic peaks of PPy, proving that PPy was effectively deposited on
the skeleton of MF.
CV measurements were performed for MF and PPy-MF (Fig. S4). The
closed area of the CV curve of MF was lower, indicating its weak conductiv-
ity and lesser capacitance (Wang et al., 2018). At a scan rate of 50 mV/s, the
specific capacitance of the PPy-MF auxiliary electrode and the MF electrode
was 34.31 F/g and 5.45 F/g, respectively. The specific capacitance of the
PPy-MF auxiliary electrode was 6.3 times higher than that of the MF elec-
trode, suggesting that the PPy-MF auxiliary electrode has a better ability
to charge and discharge the charge than the MF electrode and has the po-
tential to enhance electrokinetic remediation. Due to the existence of the
conducting polymer PPy in PPy-MF, the peak current of the CV curve
grew in size with a sizable closed region (Wu et al., 2022). Redox pairs
were observed at −0.52 V and 0.40 V. The Faraday redox reaction of PPy
on MF may be the cause of the reduction peak's somewhat greater visibility
than the oxidation peak (Beregoi et al., 2017). Electrons could be conducted
through PPy in PPy-MF, and the conductivity of PPy-MF directly affects the
redox ability of its surface (Yu et al., 2017). EIS examined the PPy-MF sur-
face's capacity to convert charges (Fig. S5). The Nyquist plot revealed that
Z. Qu et al.
Fig. 1. (a) Schematic illustration of the preparation of PPy-MF. (b-d) SEM images of MF. The SEM images (e-g) and TEM images (h-j) of PPy-MF.
the arc radius of PPy-MF was substantially lower than that of MF, suggest-
ing that the electrochemical impedance was significantly decreased, the
charge transfer was sped up, and the overall electrochemical performance
was enhanced (He et al., 2022; Wu et al., 2022).
3.2. Cr(VI) adsorption experiments
The adsorption performance of the prepared PPy-MF was investigated
after adjusting different surfactant (SDBS and CTAB) ratios and Py dose
(Fig. S6). The adsorption capacity of pore-rich MF was one order of
magnitude lower than PPy-MF at 9.3 mg/g. The high adsorption capacity
of PPy-MF indicated that the PPy particles deposited on the MF skeleton
could effectively adsorb Cr(VI) ions from the solution (Xu et al., 2019;
Zhan et al., 2018). PPy-MF-2 (C (SDBS): C (CTAB) of 1:2) showed the larg-
est adsorption capacity at different Py dosing amounts (Wang et al., 2019b).
With an increase in Py dose, the total adsorption capacity of PPy-MF tended
to rise, then decrease. The adsorption capacity of PPy-MF-2 peaked at
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Science of the Total Environment 876 (2023) 162840
140.2 mg/g when the dosage of PPy-MF was 2 mL. The adsorption capacity
decreased at a Py dosage of 2.5 mL. A plausible explanation was that the ag-
gregation of PPy particles led to the obstruction of the PPy-MF pores, which
affected the interfacial reaction between the PPy-MF surface and the solu-
tion. A Py dosing amount of 2 mL of PPy-MF-2 was selected for subsequent
experiments.
The impact of adsorption duration on the adsorption capacity of PPy-
MF was depicted in Fig. 2a for starting Cr(VI) concentrations of 50, 75,
and 100 mg/L. Due to the saturation of the adsorption active site, the ad-
sorption processes for various initial Cr(VI) concentrations all saw a rise
in adsorption capacity for a brief period in the early stages and a progressive
approach to adsorption equilibrium in the later stages. Additionally, a
larger initial Cr(VI) concentration may offer a stronger adsorption driving
force, increasing PPy-MFs potential for adsorption (Xu et al., 2019). The
kinetic data of PPy-MF were investigated using pseudo-first-order and
pseudo-second-order models. The Weber-Morris intraparticle diffusion
model was used to analyze the rate-limiting factors in the Cr(VI) adsorption
Z. Qu et al.
Fig. 2. Kinetics of Cr(VI) sorption onto PPy-MF from simulated solutions with different initial concentrations (a), Pseudo-first-order kinetic model for adsorption of Cr(VI) by
the PPy-MF (b), Pseudo-second-order kinetic model for adsorption of Cr(VI) by the PPy-MF (c), intraparticle diffusion model for adsorption of Cr(VI) onto PPy-MF (d).
process of PPy-MF. The linearized equations of the kinetic model were
presented by Eqs. (2), (3), and (4).
k1
log ðqe  qt Þ ¼ log qe  t (2)
2:303
t 1 1 the surface of PPy-MF in a relatively short time. The second linear stage de-
¼ þ t (3)
qt k2 q2e qe
1
qt ¼ ki t2 þ C i (4)
where k1 (min−1), k2 (g·mg−1·min−1), and ki (mg·g−1·min1/2) are the
pseudo-first-order kinetic model, the pseudo-second-order kinetic model,
and the intraparticle diffusion rate constant, respectively, and qe (mg/g)
and qt (mg/g) are the amounts of Cr(VI) adsorbed at adsorption equilibrium
and at time t, respectively.
Fig. 2b-d show the linear plots of the three models mentioned above,
and the parameters calculated by the kinetic model are listed in Table S4.
The results showed that the theoretical qe values of the pseudo-second-
order kinetic model and the experimental qe (94.3–140.4 mg/g) values
were in good agreement. Furthermore, the pseudo-first-order kinetic
model's correlation coefficient (R2) varied from 0.7468 to 0.8742, which
was lower than the pseudo-second-order kinetic model's R2 value
(0.9995–0.998). These findings suggested that the adsorption of Cr(VI) by
PPy-MF was compatible with a pseudo-second-order kinetic model and
that chemical adsorption controlled the rate of the whole reaction (Han
et al., 2021; Long et al., 2021). Because k2 has a smaller value at high initial
Cr(VI) concentrations than it does at low initial Cr(VI) concentrations, PPy-
MF can exhibit higher adsorption rates for low initial Cr(VI) concentrations
(Chen and Pan, 2021; Guo et al., 2021). The linear diagram of the
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Science of the Total Environment 876 (2023) 162840
intraparticle diffusion model contains two linear stages (Fig. 2d). The re-
sults of the linear fit do not go through the origin of the coordinates, sug-
gesting that the entire adsorption response process has two mechanisms:
surface adsorption and intraparticle diffusion (Long et al., 2021). The first
linear stage was attributed to the transient diffusion of Cr(VI) in the bound-
ary layer of PPy-MF, where a significant quantity of Cr(VI) was adsorbed on
scribed the stabilization process of the diffusion of Cr(VI) into the interior,
where the diffusion process led to a decrease in the adsorption rate. The re-
sults indicated that intraparticle diffusion plays a major limiting role. The
intraparticle diffusion rate constants ki (0.7653–0.9003) and boundary
layer thickness Ci (68.1–110.1) for different initial Cr(VI) concentrations.
Both ki and Ci are relatively large, which can be reasonably explained by
the fact that the surface diffusion of Cr(VI) controls the rate of the entire re-
action (Bhaumik et al., 2016; Chen and Pan, 2021; Xu et al., 2019).
The XPS analysis of PPy-MF is shown in Fig. 3. Before the adsorption of
Cr(VI), the full scan XPS spectra of PPy-MF show distinct peaks for Cl 2p
(199.21 eV), C 1 s (285.00 eV), N 1 s (400.37 eV), and O 1 s (532.4 eV).
As shown in Fig. 3a, after the adsorption of Cr(VI) by PPy-MF, in addition
to the detected peaks of Cl 2p (199.02 eV), C 1 s (285.09 eV), N 1 s
(400.14 eV) and O 1 s (531.8 eV), the additional peaks at 586.88 and
577.04 eV can be attributed to the Cr 2p1/2 and Cr2 p3/2 characteristic
peaks (Chigondo et al., 2019; Li et al., 2020). The primary cause of the
drop in the percentage of Cl 2p atoms from 10.06 % to 7.23 % was the Cl
2p doped in PPy-MF during the preparation process would exchange ions
with the Cr(VI) oxyanions in solution (Zhang et al., 2022a). As shown in
Fig. 3b, a split-peak fit was performed for Cr 2p, and the Cr 2p spectrum
consisted of two sets of peaks, Cr 2p1/2 (586.8 eV) and Cr 2p3/2
(577.3 eV), respectively. Peaks at 577.2 and 586.8 eV are associated with
Cr(III), whereas those at 579.5 and 589.2 eV are associated with Cr(VI).
Z. Qu et al. Science of the Total Environment 876 (2023) 162840

Fig. 3. XPS survey scans of the PPy-MF before and after Cr(VI) adsorption (a), Cr 2p spectrum of the PPy-MF after Cr(VI) adsorption (b) and N 1 s spectrum of the PPy-MF
before and after Cr(VI) adsorption (c). (I: before adsorption, II: after adsorption).

The percentages of Cr(VI) and Cr(III) are 27.8 % and 72.2 %, respectively, (45 V), and EK6 (60 V) were as high as 50 mA, 70 mA, and 114 mA, respec-
showing that PPy-MF has good Cr(VI) reduction ability (Li et al., 2020). tively. This is reasonably explained by the conducting polymer's inclusion
The N 1 s core-level spectrum of the initial PPy-MF (Fig. 3c(I)) peaks at increasing the soil's electrical conductivity (EC) by discharging a significant
399.90, 400.03, and 402.47 eV correspond to the quinonoid imine group quantity of charge (Wang et al., 2022; Wang et al., 2019b). It could be ob-
(=NH-), the benzenoid amine group (-NH-), and the polaron-charged served that the current variation for all the tests went through two stages. In
imine group (-NH+-), respectively (Chigondo et al., 2019; Li et al., 2020; the first stage, the electrolysis of water produces large amounts of H+ and
Wang et al., 2015; Zhang et al., 2022a). Following the adsorption of Cr OH− ions, and the directional migration of the desorbed metal ions from
(VI) by PPy-MF, the binding energies of = NH-, -NH-, and -NH+- were the soil under the constant voltage electric field, resulting in a sharp in-
found to be 398.62, 399.64, and 402.06 eV, respectively (Fig. 3c(II)). Cr crease in the current to peaks (33, 147, 42, 203, 72, and 226 mA). This
(VI) oxidized -NH- to = NH- in PPy, which increased the percentage of
the = NH- group from 23.6 % to 31.6 %, and the proportion of the -NH-
group fell from 43.8 % to 15.2 % (Chen and Pan, 2021; Guo et al., 2021).
Furthermore, due to the oxidation of the -NH- group into the -NH+-
group, the fraction of the -NH+- group rose from 32.6 % to 53.2 %
(Bhaumik et al., 2016; Chigondo et al., 2019). The -NH+- group can bind
to the negatively charged chromium-containing species in solution by mu-
tual attraction through electrostatic interaction (Chen and Pan, 2021;
Zhang et al., 2022a). Only the percentage of the -NH- group decreased, in-
dicating that it played the role of electron donor (Chen and Pan, 2021).

3.3. Variation of electric current and electric potential

3.3.1. Electrical current variations in EKR

The current for three sets of EKR experiments with various voltage gra-
dients is shown in Fig. 4. Current intensity influenced the mobility of heavy
metal ions in the soil directly (Chu et al., 2022). In the presence of MF, the
initial currents of EK1 (30 V), EK3 (45 V), and EK5 (60 V) were 4 mA,
10 mA, and 22 mA, respectively, and the initial currents were all very
low. The main reason is that the electrode solution has not yet entered
the soil and the metal ions in the soil need time to dissolve and desorb, so
the soil resistance is large (Ghobadi et al., 2020; Nasiri et al., 2020). How-
ever, when PPy-MF was present, the initial currents of EK2 (30 V), EK4 Fig. 4. Electric current variations during the EKR process.

6
Z. Qu et al.
process is considered to be the main stage of desorption and removal of
chromium ions from the soil, as well as the movement of Cr(III) in different
forms due to the entry of the electrolyte solution into the soil (Prakash et al.,
2019). In the second stage, due to the directional migration of mobile ions
(minerals and heavy metals) to the electrode chamber, the concentration of
mobile ions in the soil declines, and the current in the EKR experiment
gradually decreases (Fu et al., 2017). Moreover, chromium ions and other
metal ions in the soil will precipitate and adsorb on the surface of the soil
particles when the OH− ions generated by the cathode migrate toward
the anode, increasing soil resistance (Zhang et al., 2010). The current
peaks of EK2 (30 V), EK4 (45 V) and EK6 (60 V) appear at different
times, reaching peaks at 48 h, 24 h and 12 h, respectively. The driving
force of the electric field is stronger and the rate of dissolution, desorption,
and migration of the metal ions in the soil is faster when the voltage
gradient is higher. The rate of charge release is also accelerated at high
voltage gradients by the characteristics of PPy-MF, which causes a large
rise in the concentration of charged ions. As a result, with the larger voltage
gradient, the current in the EKR process hits the peak first (Fan et al., 2017).
The intensity of current directly affects the removal efficiency of heavy
metals in soil. EK2, EK4, and EK6 could maintain high current strength
for a long time compared to EK1, EK3, and EK5, allowing for complete
heavy metal removal from highly resistive contaminated soil (Ghobadi
et al., 2021).
3.3.2. Change of potential before and after the EKR
The key to the effect of EKR is that the electric field intensity directly de-
pends on the distribution of electric potential (Wang et al., 2021a). Using
the anode as the potential zero point, the potential difference between
the potential electrode and the anode (as the potential at that point) was
measured for each soil section of the initial 0 h and the end 96 h of all
EKR experiments, as shown in Fig. 5. At 0 h (Fig. 5a), the potential differ-
ence between each potential electrode points of soil for EK1, EK3, and
EK5 was not significant, and most of the voltage was shared between S1
and the anode and between S5 and the cathode. The primary cause is that
the anode and cathode use deionized water as the electrolyte, and the cur-
rent is small due to the large resistance, which is consistent with the initial
current. However, the uniform distribution of the potentials of EK2, EK4,
and EK6 caused by PPy strengthened the effective electric field, which
benefited EKR. This is explained by the fact that the charge released by
PPy improves the conductivity of the soil, and the reactor as a whole is sim-
ilar to a conductor with uniformly distributed resistance. At 96 h (Fig. 5b),
the potential difference between S1 and S2 near the anode was smaller for
all EKR experiments due to the significant number of heavy metal ions and
charged ions electromigration near the anode chamber and the increase in
conductivity. Overall, the concentration of mobile ions at points away from
the anode decreased and the resistance became larger at the end of the ex-
periment, leading to an increase in the voltage gradient between the points
Fig. 5. Electric potential variations during the EKR for different systems at 0 h (a) and 96 h (b).
7
Science of the Total Environment 876 (2023) 162840
away from the anode and a similar trend in the potential distribution for
each reactor.
3.3.3. Electric field simulation
The electric field was simulated for 0 h for all EKR experiments, and the
electric field and equipotential surface were visualized as shown in Fig. S7.
In EK2, EK4 and EK6, the electric field equipotential surface was uniformly
distributed, equivalent to the superposition of multiple uniform electric
fields, charged ions were subjected to the electric field force magnitude
does not vary significantly. However, the electric field equipotential sur-
faces in EK1, EK3, and EK5 were disorderly distributed, and the equipoten-
tial surfaces near the electrodes were denser than in the middle of the soil
chamber, implying that the effect of EKR is not consistent in the whole sys-
tem. The existence of PPy optimizes the electric field of the entire reactor,
and PPy-MF exists as an auxiliary electrode since the disordered electric
field would cause unexpected changes in the direction and rate of
electromigration in the soil (Chu et al., 2022). Combining the potential
data of each EKR experiment at 0 h (Table S5), the potential differences be-
tween S1 (at 5 cm from the anode) and S5 (at 25 cm from the anode) in EK1,
EK3, and EK5 were very small, 4.3 V, 3.72 V, and 11.25 V, respectively.
However, the potential differences between S1 and S5 in EK2, EK4, and
EK6 (20.73 V, 26.89 V, and 44.29) were 4.82, 7.23, and 3.94 times higher
than those in EK1, EK3, and EK5, respectively. This demonstrates that PPy
plays a great role in the enhancement of the effective electric field in the soil
chamber, providing sufficient power to increase the electromigration rate.
3.4. Changes of electrolyte and soil EC
3.4.1. EC change of electrolyte during EKR
The variation of EC with time for the anolyte and catholyte for all EKR
experiments is shown in Fig. 6a. EC directly correlates with the quantity
and potency of soluble charged ions in solution (Tang et al., 2020; Xu
et al., 2022). Protons and hydroxide ions are produced during the electrol-
ysis of water, increasing the EC of both the anolyte and the catholyte
(Henrique et al., 2022). The EC of the anolyte and catholyte of EK1, EK3,
and EK5 changed little. However, the EC of the NEK electrolyte with PPy-
MF present but not energized was consistently higher than that of
EK1, EK3, and EK5, due to the improved EC of the electrolyte by the release
of charge from PPy. A portion of the chromium-containing ions
electromigration to the anode chamber was likely adsorbed to the PPy-
MF since the EC of the EK2, EK4, and EK6 anode solutions grew fast to
their highest values of 50.3 mS/cm, 51.0 mS/cm and 63.4 mS/cm, respec-
tively, during the early stage of EKR. The EC of the anolyte is always greater
than the EC of the catholyte and thus has a prevailing influence. A reason-
able explanation is that a large amount of charged ions and Cr(VI) oxygen-
ated anion complexes (Cr2O2− 7 and CrO2−4 ) in the system can gradually
accumulate near the anode through electromigration and electroosmosis,
Z. Qu et al.
Fig. 6. Electrolyte electrical conductivity (a) and pH (c) variations during the EKR. Soil electrical conductivity (b) and pH (d) variations after the EKR.
while only a small amount of ions rely on electromigration to enter the cath-
ode (Tang et al., 2020; Tang et al., 2021).
3.4.2. Changes in soil EC before and after EKR
The EC of the S1-S5 interval of the soil before and after all EKR experi-
ments is shown in Fig. 6b. Compared with the initial EC of the contami-
nated soil (261.8 μS/cm), the EC of each interval of the soil chamber of
EK1, EK3, and EK5 decreased, indicating that there was no additional
charge replenishment during this traditional EKE process, and the EC of
the soil decreased seriously, which was not favorable for the long-term
operation of EKR. The EC of EK2, EK4, and EK6 at S1-S4 was observed to
decrease, and the conductivity at S4 near the cathode was lower than that
of the initially contaminated soil. This could be ascribed to the migration
of a mass of anions to the anode for enrichment during the EKR proceeds,
whereas the heavy metal cations migrating to the vicinity of the cathode
would continuously generate OH− ions with the cathode chamber to
produce hydroxide precipitates. The combined effect of the above two as-
pects leads to a low EC at S4 (Gao et al., 2020; Wen et al., 2021; Xu et al.,
2022). Moreover, it was discovered that for EK2, EK4, and EK6, the EC in
the soil decreased with increasing voltage gradient, indicating that a larger
voltage gradient can cause more ions to migrate from the soil to the elec-
trode chamber.
3.5. Electrolyte and soil pH variation
3.5.1. Electrolyte pH changes during EKR
The variation of pH with time for the anolyte and catholyte for all EKR
experiments is shown in Fig. 6c. The pH of the electrolyte regulates the ad-
sorption of heavy metal ions on PPy-MF adsorption sites (Xu et al., 2019).
The initial pH of the anolyte and catholyte of NEK without electricity is
2.07 and 2.31, and the pH decreases slightly with time to maintain around
1.77–1.95. It makes sense to assume that PPy from a strong Lewis acid can
8
Science of the Total Environment 876 (2023) 162840
make the electrolyte's pH acidic, which has a favorable impact on EKR
(Azioune et al., 2002; Zhan et al., 2018). On the one hand, due to the higher
current of the EK2, EK4, and EK6 systems, the electrolytic water rate was
faster and more H+ and OH− ions were produced; on the other hand,
due to the influence of the strong Lewis acidity of PPy, the pH of the EK2,
EK4, and EK6 anolytes was eventually lower than that of the EK1, EK3,
and EK5 anolytes. It is noteworthy that although the pH of all energized
EKR experimental catholyte eventually stabilized around 12.74, we ob-
served that the pH of EK2, EK4, and EK6 catholyte changed from acidic
to alkaline. The pH of EK1, EK3, and EK5 catholyte was strongly alkaline
at the beginning and stabilized quickly, which means that the presence of
PPy can buffer the polarization of catholyte pH to weaken the negative im-
pact of the focusing effect.
3.5.2. Changes of soil pH
The pH of the S1-S5 interval of the soil before and after all EKR experi-
ments is shown in Fig. 6d. In soil, the existing pattern of Cr(VI) in the soil is
controlled by the pH value. When the pH value is 1–5, HCrO− 4 is the main
form, and there is a small quantity of Cr2O2− 7 . The dominating form of Cr
(VI) changes to CrO2− 4 as the pH rises, and HCrO− 4 is easier to adsorb on
PPy-MF adsorption sites than CrO2− 4 . Additionally, high pH denotes intense
OH− competition for adsorption sites, which would further prevent mutual
adsorption of CrO2−4 and PPy (Baral et al., 2006; Xu et al., 2019). Compared
with the initial contaminated soil pH (7.27), the pH of S1 and S5 of NEK
close to the anode and cathode chambers decreased slightly and were
weakly acidic, which was consistent with the NEK electrolyte pH. Gradu-
ally, the pH of the soil increased toward anode to cathode in all energized
EKR experiments, which is still mostly attributable to the influence of elec-
trolytic water. In terms of overall residual soil pH, EK2, EK4, and EK6 had
lower soil pH than EK1, EK3, and EK5, and the area where the pH was
acidic was larger because H+ migrated at a faster rate than OH− (Zhang
et al., 2022d). The alkali front in EK1, EK3, and EK5 dominated, while
Z. Qu et al.
the acid front in EK2, EK4, and EK6 dominated, indicating that PPy could
inhibit the development of alkali front and aid in enhancing the activity
of heavy metal ions in their migration. The high pH of S4 and S5 near the
cathode tends to generate hydroxide or carbonate precipitation leading to
a decrease in EC, in agreement with the results of soil conductivity (Nasiri
et al., 2020).
3.6. Effect of PPy-MF on soil EKR results
3.6.1. Concentration of total Cr in the electrode chamber after EKR
Fig. 7a displays the electrolyte's total Cr concentration in the electrode
chambers of each system following EKR. Lower total Cr concentrations
were detected in the electrode chambers of the NEK because Cr in the soil
diffused into the electrode chamber through pore water. It is evident that
the anode chamber of the electrified EKR experiment has a greater total
Cr content than the cathode chamber, and that only a tiny amount of the
Cr in the soil beside the cathode chamber diffuses into the cathode cham-
ber. Moreover, the total Cr concentration in the anode chamber was posi-
tively correlated with the voltage gradient, which was attributed to the
higher voltage gradient providing a greater driving force resulting in a
higher Cr enrichment near the anode. The total Cr concentrations in the
anode chambers of EK1, EK3, and EK5 were 1478.2, 1954.5, and
2283.5 mg/L, while EK2 (242.9 mg/L), EK4 (318.7 mg/L), and EK6
Fig. 7. (a) The total Cr concentration of the electrolyte in the electrode chamber of each system after the EKR, and the illustration is the magnification of the total Cr
concentration of the catholyte. Standard concentrations of (b) total Cr and (c) Cr(VI), and (d) the proportion of Cr(VI) to total Cr at different intervals.
9
Science of the Total Environment 876 (2023) 162840
(572.4 mg/L) were only 16.43 %, 16.31 %, and 25.07 % of those of EK1,
EK3, and EK5 at the same voltage gradient. The main reason was that the
presence of PPy adsorbed massive Cr that migrated to the anode and
immobilized Cr on PPy-MF reducing the risk of Cr re-entry into the soil.
3.6.2. Residual distribution of total Cr and Cr(VI) after EKR
Fig. 7b shows that the total Cr concentration in the soil is distributed
step-like after the energized EKR experiment. The total Cr was mainly accu-
mulated at S1 near the anode. EK2, EK4, and EK6 concentrations at S1 were
lower than EK1, EK3, and EK5 concentrations at the same voltage gradient.
The main reason was that the presence of PPy-MF caused more Cr to mi-
grate to the anode chamber and immobilized Cr on PPy-MF, so the total
Cr concentration accumulated at S1 was relatively low. The average total
Cr removal rates of EK1-EK6 were 26.7 %, 35.9 %, 36.0 %, 45.4 %,
37.3 %, and 46.7 %, respectively. The average removal rate of total Cr
rose significantly when the voltage increased from 30 V to 45 V, while
the removal rate increased slightly when the voltage increased from 45 V
to 60 V, which may be due to the side effects of high current (Wen et al.,
2021). Notably, the average total Cr removal rate of EK2 (30 V) is approx-
imately equal to that of EK3 (45 V), implying that the use of PPy-MF can
achieve the effect of traditional EKR high voltage work under low voltage
supply conditions, saving electricity costs. Fig. 7c can be visualized that
the residual Cr(VI) concentrations of EK2, EK4, and EK6 are lower than
Z. Qu et al.
those of EK1, EK3, and EK5 at the same voltage gradient. The average Cr
(VI) removal rates of EK1-EK6 were 74.7 %, 83.3 %, 84.4 %, 92.9 %,
86.0 %, and 94.5 %, respectively. PPy-MF promoted more Cr(VI) migration
to the anode chamber and benefited EKR. The ratio of Cr(VI) to total Cr in
all experimental S1-S5 soil intervals is shown in Fig. 7d. Discovered that the
reduction rate of Cr(VI) in EK2, EK4, and EK6 is overall higher than that in
EK1, EK3, and EK5. PPy-MF increased the reduction rate of Cr(VI), which
helped to reduce the overall toxicity of Cr in soil. Furthermore, even though
total Cr accumulated at S1 near the anodes of EK2, EK4, and EK6, the pro-
portion of Cr(VI) was low, indicating that massive Cr(VI) was reduced.
3.6.3. Cr speciation variations after EKR
The chemical speciation of Cr in soil affects the migration rate and re-
moval efficiency (Tang et al., 2020). Fig. S8 displays the chemical specia-
tion of Cr in each interval of EK1-EK6 soil following EKR. The initial
contaminated soil included 46.83 %, 16.32 %, 34.01 %, and 2.84 % of
the F1, F2, F3, and F4 fractions of Cr, respectively. The proportion of F1
fraction in EK1-EK6 soils decreased substantially, while the proportion of
F2, F3, and F4 fractions increased. The F3 fraction was the highest of all
Cr fractions, probably forming chromium-containing complexes with or-
ganic matter (Ignatowicz, 2017; Li et al., 2019). The F1 fraction was the eas-
iest to remove. The percentage of F1 fraction at S3 of EK2, EK4, and EK6
was as low as 4.19 %, 2.53 %, and 3.68 %, while the lowest percentage of
F1 fraction in EK1, EK3, and EK5 was 6.52 %, 6.17 %, and 4.09 %, which
could be attributed to the presence of PPy leading to greater current to pro-
mote the removal of F1 fraction. The average percentages of F2 fractions of
S1-S5 in EK2, EK4, and EK6 were 19.40 %, 23.53 %, and 25.76 %, respec-
tively, which were 5.53 %, 13.16 %, and 17.87 % higher compared to EK1
(18.38 %), EK3 (20.80 %), and EK5 (21.86 %), respectively. The relatively
poor stability of the F2 fraction suggests that PPy-MF can improve the de-
crease in heavy metal mobility caused by traditional EKR. Furthermore,
EK1, EK3, and EK5 had average F4 fractions in S1-S5 percentages of
9.66 %, 10.23 %, and 10.42 %, respectively, which were slightly higher
than those in EK2 (6.72 %), EK4 (7.09 %), and EK6 (8.01 %). F4 fraction
can be stable in the soil and difficult to remove, the use of PPy-MF reduces
the conversion of Cr into residue state and facilitates more complete re-
moval of Cr by EKR (Tang et al., 2020). Overall, the introduction of the aux-
iliary electrode PPy-MF in EKR facilitated the complete removal of heavy
metals from the soil.
3.7. XPS variation of PPy-MF before and after EKR
XPS analysis of MF of the EK1 anode and PPy-MF of the EK2 anode after
EKR is shown in Fig. 8. The Cr 2p peak intensity of PPy-MF is much higher
Fig. 8. Cr 2p spectrum of (a) MF and (b) PPy-MF after the EKR.
10
Science of the Total Environment 876 (2023) 162840
than that of MF, implying that PPy-MF assisted EKR can enrich the
adsorption of more Cr species than traditional EKR (Wang et al., 2019b).
For the Cr 2p spectrum of MF (Fig. 8a), the peaks at 579.5 and 589.2 eV cor-
respond to Cr(VI), and the sum of the two parts still accounts for 30.5 % of
the total Cr. Nevertheless, PPy-MF can reduce Cr(VI) by the electron-rich
PPy portion, so the percentage of Cr(VI) corresponding to the 579.5 and
589.2 eV energy bands in the Cr 2p spectrum of PPy-MF is 17.2 %, indicat-
ing that most of the Cr(VI) migrating to the anode chamber can be adsorbed
by PPy-MF and reduced to Cr(III) to immobilize on PPy-MF (Fig. 8b). Com-
pared with traditional EKR, PPy-MF can enhance the reduction capacity of
EKR systems and has good application prospects in the treatment of
contaminated soil.
4. Conclusions
In this study, auxiliary electrodes were prepared using conductive poly-
mers PPy and MF and then placed in Cr(VI)-contaminated soil to investigate
the mechanism of PPy-MF auxiliary electrodes to enhance EKR in real soil
conditions. Excellent electrochemical performance is displayed by the
PPy-MF auxiliary electrode during the EKR process, which can boost the
system's current strength, optimize the distribution of the electric field,
and resolve the low EC issue with traditional EKR soil. Additionally, PPy-
MF may buffer the polarization of the pH of the catholyte as well as prevent
the development of an alkali front in the EKR process, which is beneficial to
the removal of heavy metals from the soil. PPy-MF could improve the aver-
age removal rate of total Cr and Cr(VI) in soil of electrokinetic remediation
system, indicating that PPy-MF auxiliary electrode promoted the
electromigration of heavy metals in soil, which promoted a theoretical
basis for improving the efficiency and applicability of electrokinetic reme-
diation technology. PPy-MF as an adsorbent could significantly adsorb
and reduce Cr(VI) in the soil, which not only played a fixed role in Cr(VI)
in the soil but also reduced the possibility of secondary contamination.
The findings demonstrate that PPy-MF auxiliary electrodes prepared
based on conducting polymers enhance the ability of EKR of Cr(VI)-contam-
inated soil and expanded the ideas for soil heavy metal remediation.
CRediT authorship contribution statement
Zhengjun Qu: Conceptualization, Methodology, Validation, Visualiza-
tion, Writing – original draft, Writing – review & editing. Lihui Huang:
Project administration, Resources, Supervision. Mengmeng Guo: Investi-
gation, Methodology, Validation. Ting Sun: Formal analysis, Methodology,
Writing – original draft. Xiaoshen Xu: Writing – review & editing.
Zhenhui Gao: Project administration, Supervision.
Z. Qu et al.
Data availability
The data that has been used is confidential.
Declaration of competing interest
The authors declare that they have no known competing financial inter-
ests or personal relationships that could have appeared to influence the
work reported in this paper.
Acknowledgments
We thank Chengjia Zhang and Nannan Dong of the Core Facilities for
Life and Environmental Sciences, State Key laboratory of Microbial Tech-
nology of Shandong University for Inductively Coupled Plasma Mass Spec-
trometer analysis.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.scitotenv.2023.162840.
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